Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

网络:校园思想政治工作的新空间与新挑战

介绍了在计算机、互联网为代表的第三次产业革命冲击下 ,网络带给校园思想政治工作的机遇与挑战 ,提出了在网络环境下从事该项工作的策略及建议     

我国未来电信监管模式的新探索

电信产业的快速发展和电信技术的不断创新给电信监管带来了巨大的挑战。为此,本文从分析电信业发展的趋势和由此对电信监管带来的挑战入手,在对国外电信监管模式和技术手段进行充分实证分析的基础上,从政策法律、市场准入、互连互通、资费管制、普遍服务、电信标准等六个方面探讨了我国未来电信监管模式的发展方向和发展趋势。     

131I治疗甲状腺机能亢进症的自然转归分析

针对采用131I治疗甲状腺功能亢进症后如何进行暂时性甲状腺机能低下症的调整、治疗问题进行了分析,为甲状腺机能低下症的调整、治疗提供了参考.     

基于Oracle Spatial的WEBGIS数据模型构造

结合WEBGIS的特征,提出了满足WEBGIS实际性能要求,便于实际实施的一种空间数据模型结构实例,解决了WEBGIS与Oracle Spatial无缝连接的问题。     

Structural characterization and ferromagnetic behavior of Fe-doped TiO2 powder by high-energy ball milling

Fe-doped TiO₂ powder was prepared by high-energy ball milling, using TiO₂ Degussa P-25 and α-Fe powders as the starting materials. The structure and magnetic properties of the Fe-doped TiO₂ powder were studied by X-ray diffraction, ⁵⁷Fe Mossbauer spectroscopy and vibrating sample magnetometer. The Reitveld refinement of XRD revealed that ball milling not only triggered incorporation of Fe in TiO₂ lattice but also induced the phase transformation from anatase to rutile in TiO₂ and consequently the milled Fe-doped TiO₂ powder contained only rutile.⁵⁷Fe Mössbauer effect measure showed that Fe atoms existed in Fe²⁺ and Fe³⁺ state, which were assigned to the solid solution Fe_xTi_1−xO₂. The magnetization measurements indicated that the milled Fe-doped TiO₂ powder was ferromagnetic above room temperature. The ferromagnetism in our milled Fe-doped TiO₂ powder seemingly does not come from Fe and iron oxides particles/clusters but from the Fe-doped TiO₂ powder matrices.     

Ⅰ类超晶格势阱中能级分布及电子跃迁规律研究

在研究大量实验曲线的基础上,指出势阱所有能级均有一定的宽度,电子或空穴在各能级中出现的概率符合正态分布,从理论上分析了I类超晶格和双势垒单势阱的发光光谱与吸收光谱·解释了GaAs/Ga1-xAlxAs多量子阱和超晶格吸收光谱吸收边及量子阱变窄时各吸收峰的“蓝移现象”及GaAs/Ga1-xAlxAs双势垒单量子阱样品的电流—电压特性曲线及电导—电压特性曲线的特征和出现的“负阻效应”·     

最小费用k度限制树对策

本在Glover—Klingman算法及最小费用支撑树对策的基础上，讨论了最小费用k度限制树对策问题．利用威胁、旁支付理论制订了两种规则，并利用优超、策略等价理论分别给出了在这两种规则下最小费用k度限制树对策核心中的解，从而证明了在这两种规则下其核心非空．